EP0423866A1 - Phosphor-Verbindungen - Google Patents

Phosphor-Verbindungen Download PDF

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Publication number
EP0423866A1
EP0423866A1 EP90202644A EP90202644A EP0423866A1 EP 0423866 A1 EP0423866 A1 EP 0423866A1 EP 90202644 A EP90202644 A EP 90202644A EP 90202644 A EP90202644 A EP 90202644A EP 0423866 A1 EP0423866 A1 EP 0423866A1
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EP
European Patent Office
Prior art keywords
pyridyl
substituted
lithium
methyl
unsubstituted aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90202644A
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English (en)
French (fr)
Inventor
Petrus Henricus Maria Budzelaar
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication date
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Publication of EP0423866A1 publication Critical patent/EP0423866A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0013—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings

Definitions

  • the invention relates to a process for the preparation of a phosphide and to processes for the preparation of phosphines from the phosphide and to phosphides and phosphines as novel compounds.
  • Certain pyridyl phosphines find application as ligands in catalysts for the synthesis of methylmethacrylate.
  • the invention relates to a process for the preparation of a phosphide of the chemical structure RPPyLi wherein R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, P is phosphorous, Py is 2- or 4-pyridyl and Li is lithium, wherein
  • the phosphides of the chemical structure RPPyLi are prepared by reaction of a lithium compound with a pyridylphosphine with at least two pyridyl groups. Depending on the groups bound to the Li-atom and the groups bound to the -PPyLi moiety, the phosphide RPPyLi has taken up the R from either the lithium compound or has kept it from the phosphine, in accordance with the reactions under a), b), c) and d) above.
  • Ar is preferably a phenyl group or a substituted phenyl group, such as 4-methoxyphenyl or 4-dimethylaminophenyl.
  • the lithium compound is preferably lithiumhydride, methyl lithium, tert.butyllithium, phenyl lithium, p-tolyl lithium or 6-methyl-2-pyridyllithium.
  • the reaction is preferably performed in the presence of a solvent.
  • Preferred solvents are tetrahydrofuran, hexane, diethylether or toluene.
  • the reaction temperature may be between -100 °C and 100 °C, preferably between -80 °C and 20 °C.
  • the starting phosphine must contain at least two 2- or 4-pyridyl groups.
  • Starting compounds having one such pyridyl group or a 3-pyridyl group do not react in the desired manner with lithium compounds and give 1,4-dihydropyridyl or 1,2-dihydropyridyl derivatives by addition to the pyridyne ring.
  • Pyrimidinyl group containing phosphines react in the same way.
  • the invention also relates to a process for the preparation of a phosphine of the chemical structure RPPyH, wherein R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, P is phosphorous, Py is 2- or 4-pyridyl and Li is lithium, in which process the phosphide of the structure RPPyLi, wherein R, P and Py have the above meanings is reacted with a proton-donating agent, such as with water; and to the obtained phosphines as novel compounds.
  • RPPyH wherein R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, P is phosphorous, Py is 2- or 4-pyridyl and Li is lithium
  • the invention further relates to a process for the preparation of a phosphine of the chemical structure RR1PyP, wherein P is phosphorous, Py is 2- or 4-pyridyl, R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, and R1 is substituted or unsubstituted alkyl or aryl, by reacting a phosphide of the chemical structure RPPyLi, wherein R, P and Py have the above meanings, is reacted with a halogenide of the formula R1Hal, wherein R1 is substituted or unsubstituted alkyl or aryl and Hal represents chlorine or bromine.
  • a phosphine of the chemical structure RR1PyP wherein P is phosphorous, Py is 2- or 4-pyridyl, R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, and R1 is substituted or un
  • RPPyLi and RPPyH wherein R is alkyl, substituted or unsubstituted aryl, 2- or 4-pyridyl, P is phosphorous, Py is 2- or 4-pyridyl, Li is lithium and H is hydrogen, are novel compounds. Specifically mentioned are those compounds wherein in both chemical structures R is methyl, n-butyl, tert.butyl, phenyl, p-tolyl, 4-methoxyphenyl, 4-dimethylaminophenyl or 6-methyl-2-pyridyl.
  • the reaction product of RPPy Li and R1Hal is a phosphine of the chemical formula RR1PPy in which R and R1 are groups which may be different. Consequently the process according to the invention has the possibility to prepare phos­phines with 3 different organic groups.
  • Phosphines with a 2- or 4-pyridyl group and two different other organic groups, wherein R is alkyl or substituted or unsubstituted aryl and R1 is substituted or unsubstituted alkyl or aryl are also novel compounds.
  • the phosphide was further characterized as the hydrolysis product, the secondary phosphine n-butyl 2-pyridylPH:
  • the reaction was carried out as described in example 1, but using 2.51 g (4-pyridyl)3P.
  • the reaction was carried out as described in example 1, but using 2.51 g (2-pyridyl)3P.
  • the lithium phosphide was characterized by 31P NMR and by hydrolysis to the secondary phosphine n-butyl 2-pyridylPH, obtained as a 1:1 molar mixture with 2,2′-bipyridine.
  • the reaction was carried out as described in example 1, but using 2.78 g (4-methoxyphenyl)(2-pyridyl)2P.
  • the lithium phosphide was characterized by 31P NMR and by hydrolysis to the secondary phosphine (n-butyl)(2-pyridyl)PH, obtained as a 1:1 molar mixture with 2-(4-methoxyphenyl)-pyridine in 80% yield.
  • the (4-methoxyphenyl)(2-pyridyl)2P starting material was prepared as follows:
  • reaction was carried out as described in example 1, but using 2.51 g (2-pyridyl)3P NMR and a suspension of 0.10 g LiH in 10 ml hexane.
  • the reaction was also carried out at a temperature of 45 °C and the reaction time was 1 hour.
  • the reaction was carried out as described in example 5, but using 2.50 g phenyl(2-pyridyl)2P.
  • the reaction was carried out as described in example 7, except that the solvent used for the phenyl(2-pyridyl)2P was toluene.
  • the hydrolysis product contained methyl 2-pyridylPH, phenyl 2-pyridylPH, dimethyl 2-pyridylP and 2-phenylpyridine in the approximate ratio 36:52:11:40, as well as traces of dimethyl phenyl phosphine and methyl phenyl 2-pyridyl phosphine.
  • reaction was carried out as described in example 1, but using 2.91 g (4-dimethylaminophenyl)(2-pyridyl)2P and a solution of 0.36 g p-tolylLi in 5 ml tetrahydrofuran.
  • the reaction was carried out as described in example 1, except that the solvent was toluene, and that a cooled (-35 °C) solution of 0.94 g (6-methyl-2-pyridyl)Li in 15 ml toluene was used.
  • the (6-methyl-2-pyridyl)Li starting material was prepared as follows:
  • reaction was carried out as described in example 9, except that 2.51 g (2-pyridyl)3P was used. After hydrolysis the reaction product showed the presence of p-tolyl 2-pyridylPH, (2-pyridyl)2PH, p-tolyl(2-pyridyl)2P, 2-(p-tolyl)-pyridine and 2,2′-bipyridine in the approximate ratio 70:30:60:30:70.
  • reaction was carried out as described in example 1, except that 5.6 ml of a 1.7 M solution of t-butylLi in n-pentane was used.
  • the reaction was carried out as described in example 9, but 2.50 g of phenyl(2-pyridyl)2P was used. 31P NMR analysis of the reaction mixture showed the formation of phenyl 2-pyridylPLi and p-tolyl 2-pyridylPLi; hydrolysis afforded a mixture of p-tolyl 2-pyridylPH, phenyl 2-pyridylPH, 2-(p-tolyl)-pyridine and 2-phenylpyridine in the approximate ratio 27:23:23:27 and 90% yield.
  • reaction was carried out as described in example 7, but 2.51 g of (2-pyridyl)3P was used. Analysis of the reaction mixture by 31P NMR showed the formation of methyl 2-pyridylPLi and (2-pyridyl)2PLi as well as some dimethyl 2-pyridylP; hydrolysis afforded a mixture of methyl 2-pyridylPH, (2-pyridyl)2PH, (methyl)2 2-pyridylP and 2,2′-bipyridine in the approximate ratio 30:10:10:50.
  • n-butyl 2-pyridylPLi was prepared as described in example 1. This solution was, however, not hydrolyzed. Instead, it was cooled to -40 °C and a solution of 1.3 g 1-bromobutane in 10 ml tetrahydrofuran was added. The mixture was again warmed to room temperature, the solvents were removed in vacuo, and 25 ml of diethylether and 10 ml of water were added. After 10 min of stirring, the organic layer was separated and the water layer was extracted with 10 ml of ether. The organic layers were combined and the solvent was removed in vacuo (66 Pa).
  • the reaction was carried out as described in example 17, except that a 1.6 M solution of methylLi in diethylether was used instead of the n-butylLi solution, and 1.3 g iodomethane instead of the bromobutane.
  • the reaction product was a mixture of (methyl)2 2-pyridylP, methyl phenyl 2-pyridylP and 2-phenyl pyridine in the approximate ratio 70:30:60, from which the (methyl)2 2-pyridylP was isolated by distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Catalysts (AREA)
EP90202644A 1989-10-20 1990-10-04 Phosphor-Verbindungen Withdrawn EP0423866A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898923683A GB8923683D0 (en) 1989-10-20 1989-10-20 Phosphorus compounds
GB8923683 1989-10-20

Publications (1)

Publication Number Publication Date
EP0423866A1 true EP0423866A1 (de) 1991-04-24

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EP90202644A Withdrawn EP0423866A1 (de) 1989-10-20 1990-10-04 Phosphor-Verbindungen

Country Status (6)

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EP (1) EP0423866A1 (de)
JP (1) JPH03167196A (de)
KR (1) KR910007944A (de)
BR (1) BR9005252A (de)
CA (1) CA2027923A1 (de)
GB (1) GB8923683D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266307A (ja) * 2007-03-29 2008-11-06 Sumitomo Chemical Co Ltd 新規ホスフィンおよびその製造方法と用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0271144A2 (de) * 1986-12-05 1988-06-15 Shell Internationale Researchmaatschappij B.V. Carbonylierungsverfahren von ungesättigten Acetylenverbindungen
EP0386834A1 (de) * 1989-03-03 1990-09-12 Shell Internationale Researchmaatschappij B.V. Katalytisches System für Karbonylierung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0271144A2 (de) * 1986-12-05 1988-06-15 Shell Internationale Researchmaatschappij B.V. Carbonylierungsverfahren von ungesättigten Acetylenverbindungen
EP0386834A1 (de) * 1989-03-03 1990-09-12 Shell Internationale Researchmaatschappij B.V. Katalytisches System für Karbonylierung

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMISCHE BERICHTE, vol. 123, no. 5, May 1990, pages 989-993, VCH Verlagsgesellschaft mbH, Weinheim, DE; G.U. SPIEGEL et al.: "Synthese und Reaktionen von 2-Pyridylphosphan, 2-C5NH4-PH2" *
HETEROCYCLES, vol. 30, no. 1, 1990, pages 347-351; Y. UCHIDA et al.: "Reaction of triheteroarylphosphines with organolithium reagents concurrent ligand exchange and ligand coupling" *
JOURNAL OF ORGANIC CHEMISTRY, vol. 43, no. 5, 3rd March 1978, pages 947-949, American Chemical Society; G.R. NEWKOME et al.: "Chemistry of hetercyclic compounds. 27. An improved preparation of pyridyldiphenylphosphines" *

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KR910007944A (ko) 1991-05-30
BR9005252A (pt) 1991-09-17
GB8923683D0 (en) 1989-12-06
CA2027923A1 (en) 1991-04-21
JPH03167196A (ja) 1991-07-19

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